JP2001062261A - Spiral type gas-liquid contact membrane element and spiral type gas-liquid contact membrane module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spiral type gas-liquid contact membrane element which obviates the occurrence of the degradation in the concentration of a gaseous solution and the intrusion of air bubbles into the gaseous solution by rapidly discharging the condensed water in a gas side flow passage and a spiral type gasliquid contact membrane module. SOLUTION: Two sheets of gas side flow passage materials are disposed in channel parts along the flow direction of gaseous ozone and are arranged in spiral type membrane elements 10 in such a manner that the channel parts face each other. The gaseous ozone is supplied from a gas inlet 11a into a gas supply pipe 11, passes the spiral gas side flow passages 18 from supply holes 11b and is discharged outside from a gas outlet 7. The condensed water in the gas side flow passages 18 flows together with the gaseous ozone along the channel parts of the gas side flow passage materials and is discharged outside from the gas outlet 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spiral-type gas-liquid contact membrane element used for a gas-liquid contact operation such as dissolution of a gas in a liquid or emission of a gas from a liquid, and a spiral gas-liquid membrane element using this element. The present invention relates to a liquid contact membrane module.

[0002]

2. Description of the Related Art Conventionally, in many fields such as the chemical industry, a gas-liquid contact operation such as dissolving gas into a liquid or releasing gas from a liquid is performed. For example, as gas dissolution, oxygen supply to microbial cultures in the pharmaceutical field, etc.,
Dissolution of ozone into ultrapure water lines in the electronics industry, supply of oxygen to fish farming in the fisheries industry, and treatment of exhaust gas such as NO _x (nitrogen oxide) and SO _x (sulfur oxide). Is a decarboxylation treatment in pure water production.

[0003] One example of gas-liquid contact is the production of ozone water in the semiconductor industry. At present, chemicals such as a mixed solution of ammonia-hydrogen peroxide solution and a mixed solution of hydrochloric acid-hydrogen peroxide solution are used for cleaning the wafer. However, from the viewpoint of cost reduction of wastewater treatment, environmental problems, etc. Attention has been paid to washing with water. Here, the ozone water used for cleaning the wafer requires ozone water having a high concentration of 10 to 30 ppm, and the concentration control must be easy.

In order to satisfy these conditions, the conventional so-called bubbling method has problems such as difficulty in obtaining high-concentration ionic water, problems in cleanliness, and difficulty in concentration control. In recent years, a method of dissolving ozone gas in ultrapure water using a membrane module has been used in recent years.

[0005] The form of the membrane module used for the gas-liquid contact operation includes a flat membrane module using a flat membrane such as a spiral type, a flat membrane laminated type, and a plate and frame type, and a hollow fiber. There is an annular membrane module using a simple annular membrane. Among them, hollow fiber membrane modules and spiral type membrane modules are common.

In the case of the hollow fiber membrane module, since pure water flows in a laminar state inside the hollow fiber membrane, the membrane resistance near the inner peripheral surface of the hollow fiber membrane is large, and the transfer of ozone gas to the pure water is performed. The coefficient is low. In the hollow fiber membrane module,
Since the filling efficiency of the membrane is low, the membrane module is large and the cost is high.

On the other hand, in the spiral type membrane module, by using a channel material for promoting turbulence in the liquid side channel,
The film resistance near the porous film decreases, and the transfer coefficient of ozone gas to pure water increases. Further, the spiral type membrane module has an advantage that the membrane filling efficiency is high and the membrane module can be reduced in size and the cost can be reduced.

[0008]

However, in a membrane module using a porous membrane, water vapor generated in the liquid-side flow path passes through the porous membrane and condenses in the gas-side flow path to generate condensed water. A phenomenon may occur.

In the case of a spiral type membrane module,
Since the gas-side channel material, the porous membrane, and the liquid-side channel material are superimposed and wound around the outer peripheral surface of the perforated hollow tube, the gas-side channel has a narrow space interposed between the porous membranes. Become. For this reason, it is difficult for the condensed water to quickly flow out of the gas-side flow path, and gradually accumulates in the gas-side flow path. Thereby, since a substantial gas-liquid contact area is reduced,
When used for a long time, there is a problem that the concentration of ozone water decreases.

When condensed water accumulates in the gas-side flow path, the pressure loss in the gas-side flow path increases, the pressure in the gas-side flow path becomes higher than the pressure in the liquid-side flow path, and the bubbles become liquid. A problem that occurs in the side channel also occurs.

In this case, it is necessary to stop the operation of the spiral type gas-liquid contact membrane module and evaporate the condensed water by, for example, passing dry air through the gas side flow path. However, this method has a practical problem because it is a discontinuous operation.

An object of the present invention is to rapidly discharge condensed water in a gas side flow path, thereby reducing the concentration of a gas solution and preventing air bubbles from being mixed into the gas solution. And a spiral type gas-liquid contact membrane module.

[0013]

The spiral-type gas-liquid contact membrane element according to the first aspect of the present invention is a spiral-type gas-liquid contact membrane element in which a permeable membrane and a flow path material are superimposed on the outer peripheral surface of a perforated hollow tube. A spiral-type gas-liquid contact membrane element formed by winding a plurality of gas-side flow path members provided with grooves along the flow direction of gas as a flow path material. is there.

In the spiral type gas-liquid contact membrane element according to the present invention, since a plurality of gas-side flow path members provided with grooves along the gas flow direction are stacked, the gas-flow-side flow element is generated in the gas-side flow path. Condensed water quickly flows in the plurality of grooves together with the gas. This allows the condensed water to be quickly discharged without staying in the gas-side flow path. Therefore, a decrease in the gas-liquid contact area due to the stagnation of the condensed water is prevented, so that the concentration of the gas solution does not decrease. In addition, since an increase in pressure loss in the gas side flow channel due to stagnation of condensed water is prevented,
The pressure in the gas-side flow path does not become higher than the pressure in the liquid-side flow path, and no bubbles are generated in the liquid.

Preferably, a groove is provided on one side of the gas-side flow path member. In this case, the thickness of one gas-side flow path member can be reduced, and the spiral gas-liquid contact membrane element can be downsized.

Preferably, the gas-side flow path members are overlapped so that the grooves are opposed to each other. In this case, a groove having a larger flow path can be formed, and the pressure loss in the gas-side flow path material can be further reduced.

Preferably, the groove has a continuous shape. In this case, the condensed water flows through a continuous groove from the flow start point to the end point without any obstacles. Therefore, the flow resistance of gas and condensed water in the groove is reduced.

Preferably, the groove has a linear shape. In this case, the flow path length of the groove becomes the shortest, and the flow resistance of gas and condensed water decreases. As a result, the condensed water is quickly discharged to the outside.

It is preferable that the gas-side channel material is made of a woven or knitted fabric. In this case, the groove can be easily provided in the gas-side flow path member.

It is preferable that the thickness of one gas-side channel material is 200 μm or more and 700 μm or less. When the thickness of one gas-side flow path member is smaller than 200 μm, the gas-side flow path becomes narrow, and the flow resistance of gas and condensed water increases. As a result, gas and condensed water do not flow sufficiently, so that the gas-liquid contact efficiency is reduced and condensed water cannot be sufficiently discharged. On the other hand, if the thickness of one gas-side flow path member is larger than 700 μm, the dimensions of the spiral-type gas-liquid contact membrane element increase, the material cost increases, the installation space increases, and it is uneconomical. is there.

The width of the groove is preferably 200 μm or more and 1000 μm or less. The width of the groove of the gas side channel material is 2
If it is smaller than 00 μm, gas and condensed water do not flow sufficiently, so that the gas-liquid contact efficiency is reduced and it is difficult to sufficiently discharge condensed water. On the other hand, if the width of the groove is larger than 1000 μm, the permeable membrane will be depressed in the groove, deforming the permeable membrane and narrowing the gas-side flow path.

The depth of the groove is preferably 100 μm or more and 500 μm or less. If the depth of the groove of the gas side channel material is smaller than 100 μm, gas and condensed water will not flow sufficiently, and the gas-liquid contact efficiency will be reduced, and it will be difficult to sufficiently discharge condensed water. is there. On the other hand, when the depth of the groove is larger than 500 μm, the thickness of the gas-side flow path material becomes large, so that the dimensions of the spiral type gas-liquid contact membrane element become large, the material cost becomes high, and the installation space becomes large. It is because it increases and is uneconomical.

The width of the projection between the grooves is 250 μm or more and 750 or more.
It is preferably not more than μm. If the width of the convex portion between the grooves of the gas-side flow path material is smaller than 250 μm, the strength of the gas-side flow path material decreases, and the pressure from the liquid side of the permeable membrane causes
This is because the protrusion may be crushed. on the other hand,
If the width of the convex portion is larger than 750 μm, the gas-side flow path becomes narrow, the gas-liquid contact efficiency decreases, and it becomes difficult to sufficiently discharge condensed water.

It is preferable that the gas-side channel material is made of a fluororesin. Fluororesins have durability against various gases and liquids, so that they can be applied to a wide range of fields. Particularly, since it has durability against ozone and ozone water, it can be suitably used for production of ozone water.

The permeable membrane is composed of one or more pairs of continuous or independent porous membranes, and the porous membrane is formed by sandwiching the liquid-side channel material on the inside and the gas-side channel material on the outside to form The inner peripheral side and the outer peripheral side of the liquid-side flow path formed by the liquid-side flow path material between the porous membranes are spirally wound around the outer peripheral surface of the empty tube, and are sealed. Preferably, both ends of the gas-side flow path formed by the gas-side flow path material between the porous membranes are sealed.

In this case, the gas passes through the perforated hollow tube,
The liquid flows in the spiral gas-side flow path, and the liquid flows in the liquid-side flow path from one end to the other end of the spiral-type gas-liquid contact membrane element substantially parallel to the perforated hollow tube. In this process, the gas and the liquid come into contact with each other via the porous membrane, and the permeation of the target component is performed. At this time, the condensed water generated in the gas-side flow path quickly flows through the plurality of grooves together with the gas, and is quickly discharged. Therefore, a decrease in the gas-liquid contact area due to the stagnation of the condensed water is prevented, so that the concentration of the gas solution does not decrease. In addition, since the pressure loss in the gas-side flow path due to the accumulation of condensed water is prevented, the pressure in the gas-side flow path does not become higher than the pressure in the liquid-side flow path, and bubbles are generated in the liquid. do not do.

A spiral-type gas-liquid contact membrane module according to a second aspect of the present invention contains the spiral-type gas-liquid contact membrane element according to the first aspect in a container.

In the spiral-type gas-liquid contact membrane module according to the present invention, the gas-side channel material of the spiral-type gas-liquid contact membrane element includes a plurality of channel members provided with grooves along the gas flow direction. Since they are overlapped, the condensed water generated in the gas-side flow path quickly flows in the plurality of grooves together with the gas. This allows the condensed water to be quickly discharged without staying in the gas-side flow path. Therefore, a decrease in the gas-liquid contact area due to the stagnation of the condensed water is prevented, so that the concentration of the gas solution does not decrease. In addition, since the pressure loss in the gas-side flow path due to the accumulation of condensed water is prevented, the pressure in the gas-side flow path does not become higher than the pressure in the liquid-side flow path, and bubbles are generated in the liquid. do not do.

A spiral type gas-liquid contact membrane module according to a third aspect of the present invention comprises a continuous or independent pair of porous membranes having a first flow path material on the inside and a second on the outside.
Are spirally wound around the outer peripheral surface of the perforated hollow tube to form a spiral-type gas-liquid contact membrane element, which is formed between the porous membranes by the first channel material. The inner side and the outer side of the first channel are sealed, and both ends of the second channel formed by the second channel material between the porous membranes are sealed. The spiral-type gas-liquid contact membrane element is housed in a cylindrical container, and the cylindrical container has a first fluid port at each end and a second fluid port at least at one end and the outer peripheral portion. A first space formed at each end of the spiral-type gas-liquid contact membrane element in the cylindrical container, and a second space formed at the outer peripheral side of the spiral-type gas-liquid contact membrane element in the cylindrical container. Are separated, the first space communicates with the first fluid port,
The second space communicates with a second fluid port on an outer peripheral portion of the cylindrical container, and the inside of the perforated hollow tube communicates with a second fluid port on at least one end of the cylindrical container. As the gas-side flow path material through which the gas flows in the second flow path material, a plurality of gas-side flow path materials provided with grooves along the flow direction of the gas are used in a stacked manner.

In the spiral-type gas-liquid contact membrane module according to the present invention, the first fluid is supplied into one of the first spaces from the first fluid port at one end of the cylindrical container, and the spiral-type gas-liquid The fluid flows through the first flow path formed between the porous membranes of the contact membrane element into the other first space, and is discharged to the outside through the first fluid port at the other end of the cylindrical container. Also,
The second fluid is supplied to the inside of the perforated hollow tube from the second fluid port at at least one end of the cylindrical container, and the second fluid is formed between the porous membranes of the spiral-type gas-liquid contact membrane element. The fluid flows through the flow path into the second space in the cylindrical container, and is discharged to the outside through a second fluid port formed in the outer peripheral portion of the cylindrical container.

[0031] Inside the cylindrical container, the first fluid flows substantially parallel to the perforated hollow tube, and the second fluid spirals in a direction substantially orthogonal to the first fluid via the porous membrane. Flows to The first fluid and the second fluid come into contact with each other via the porous membrane, and the permeation of the target component is performed.

When the first fluid is a gas and the second fluid is a liquid, the condensed water generated in the first flow path is perforated hollow provided in a plurality of flow path members. The fluid quickly flows along the groove parallel to the pipe, and is discharged to the outside from the first fluid port. When the second fluid is a gas and the first fluid is a liquid, the condensed water generated in the second flow path is a perforated hollow tube provided in a plurality of flow path members. Flows quickly along the groove in the direction perpendicular to the second direction, and is discharged from the second fluid port to the outside. Therefore, a decrease in the gas-liquid contact area due to the stagnation of the condensed water is prevented, so that the concentration of the gas solution does not decrease. In addition, since the pressure loss in the gas-side flow path due to the accumulation of condensed water is prevented, the pressure in the gas-side flow path does not become higher than the pressure in the liquid-side flow path, and bubbles are generated in the liquid. do not do.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of a spiral type gas-liquid contact membrane module according to the present invention will be described. In the following description, a case where ozone water is generated using ozone gas and pure water will be described.

FIG. 1 is an axial sectional view showing a spiral type gas-liquid contact membrane module according to an embodiment of the present invention, and FIG. 2 is a spiral type gas-liquid contact membrane element in the spiral type gas-liquid contact membrane module of FIG. 3 is a sectional view taken along line AA in FIG. 1, and FIG. 4 is an enlarged sectional view of a sealing portion of the spiral type gas-liquid contact membrane element in FIG.

A spiral-type gas-liquid contact membrane module 1 shown in FIG. 1 includes a cylindrical container 2 as a pressure container and a cylindrical container 2.
A spiral-type gas-liquid contact membrane element 10 inserted into the inside. The cylindrical container 2 has a cylindrical body, and a liquid inlet 4 is formed at one end 3 of the body and a gas solution outlet 6 is formed at the other end 5. One or more gas outlets 7 are formed on the outer peripheral surface of the body of the cylindrical container 2.

One end of a gas supply pipe 11 composed of a perforated hollow pipe penetrates one end 3 of the cylindrical container 2 and has a gas inlet 11a.
And the other end is sealed with a resin material 16.
A plurality of supply holes 11 are provided in the pipe wall of the gas supply pipe 11 so that the pressure loss with respect to the supply fluid flow rate can be suppressed low.
b is formed.

In FIG. 2, a spiral-type gas-liquid contact membrane element 10 has a structure in which a hydrophobic porous film 14 is superposed on both surfaces of a liquid-side flow path member 13, and two sheets are further provided on the other surface of the hydrophobic porous film 14. The gas-side flow path members 15 are overlapped and wound around the gas supply pipe 11.

Each gas-side flow path member 15 is formed with a continuous groove 15 a extending linearly in a direction perpendicular to the axial direction of the gas supply pipe 11.

It is necessary to select a material which is in contact with ozone gas or ozone water and which has not only durability against ozone but also does not elute components of the member. Generally, a fluororesin is used, and among them, a tetrafluoroethylene resin (PTFE) and a perfluoroalkoxy resin (PFA) are preferably used.
Further, depending on the application and use conditions, a vinylidene fluoride resin (PVDF) or a perfluoroethylene propylene resin (FEP) can be used.

In this embodiment, a flat membrane made of PTFE having an average pore diameter of 0.01 to 1 μm is used as the hydrophobic porous membrane 14. Further, as the liquid-side flow path member 13, PF
A net formed by plain weaving a wire made of A is used.
Further, the gas-side flow path member 15 is formed of PFA.

As shown in FIG. 3, the spiral space between the hydrophobic porous membranes 14 sandwiching the liquid-side flow path member 13 constitutes the liquid-side flow path 19. Spiral liquid side flow path 19
The inner peripheral side (side parallel to the gas supply pipe 11) and the outer peripheral side are sealed by fusion welding the hydrophobic porous membranes 14 sandwiching the liquid-side flow path material 13. . Thereby, the inner peripheral side sealing portion 21a and the outer peripheral side sealing portion 2 are provided on the inner peripheral side and the outer peripheral side of the liquid side flow path 19, respectively.
1b is formed. Therefore, the liquid side flow path 19 is a space in which pure water and ozone water can flow in the axial direction of the spiral gas-liquid contact membrane element 10. Both ends of the liquid side flow path 19 in the axial direction are open, so that pure water can flow in and ozone water can flow out.

In the present embodiment, both sides are fusion-welded with the liquid-side flow path material 13 interposed between the two hydrophobic porous membranes 14, but one hydrophobic porous membrane 14 is used. The membrane 14 may be folded, and the liquid-side channel material 13 may be inserted therebetween, and one side may be welded.

The spiral space between the hydrophobic porous membranes 14 sandwiching the two gas side flow path members 15 constitutes the gas side flow path 18. Then, as shown in FIG. 4, both ends in the axial direction of the spiral gas-side flow path 18 are sealed with a resin material 17. The space between both ends of the outer peripheral surface of the spiral-type gas-liquid contact membrane element 10 and the inner peripheral surface of the body of the cylindrical container 2 is also sealed with the resin material 17 to form a cylindrical space 18a. Thereby, sealing portions 10b and 10c are formed at both ends of the gas-side flow path 18. Therefore, the gas side flow path 18 is a space in which the ozone gas 25 can flow in the spiral direction of the spiral type gas-liquid contact membrane element 10,
The ozone gas 25 can flow out of the module from the cylindrical space 18a through the gas outlet 7.

As described above, the gas-side flow path 18 and the liquid-side flow path 19 in the gas-liquid contact portion 10a excluding the sealing portions 10b and 10c at both ends of the spiral type gas-liquid contact membrane element 10.
Is defined by the hydrophobic porous membrane 14, the outer peripheral side sealing portion 21a, the inner peripheral side sealing portion 21b, and the sealing portions 10b and 10c.
It has a separate configuration.

FIG. 5 is a schematic view showing an example of the gas-side flow path member 15 of the spiral type gas-liquid contact membrane element 10 of FIG. The gas-side channel member 15 in FIG. 5 is made of a woven fabric having a large number of continuous linear grooves 15a on both surfaces.

FIG. 6 is an enlarged sectional view of a portion B shown in FIG. As shown in FIG. 6, in the present embodiment, two gas-side flow path members 15 are stacked so that the grooves 15 a of the gas-side flow path members 15 face each other, and two hydrophobic porous membranes 14 are formed. Placed between. Accordingly, the grooves 15a of the two gas-side flow path members 15 are combined, the cross-sectional area of the space formed by the grooves 15a is increased, and the gas and the condensed water can flow sufficiently, and the gas-liquid contact efficiency can be improved. And condensed water can be sufficiently discharged.
The number of gas-side flow path members is not particularly limited to the above example, and may be another number.

5 and 6, when the thickness of one of the gas side flow path members 15 is smaller than 200 μm, the gas side flow path becomes narrow, and the flow of gas and condensed water is reduced. Resistance increases. As a result, the gas and the condensed water do not flow sufficiently, the gas-liquid contact efficiency is reduced, and the condensed water cannot be sufficiently discharged. On the other hand, when the thickness of one gas-side flow path member 15 is greater than 700 μm, the diameter of the spiral-type gas-liquid contact membrane element 10 increases,
It is uneconomical because the material cost is high. In addition, the installation space is increased, which is uneconomical. Therefore, the thickness of the gas-side flow path member 15 is preferably 200 to 700 μm.

If the width of the groove 15a is smaller than 200 μm, the gas and the condensed water do not flow sufficiently, so that the gas-liquid contact efficiency is reduced and it is difficult to sufficiently discharge the condensed water. On the other hand, when the width of the groove 15a is larger than 1000 μm, the hydrophobic porous film 14 is depressed in the groove 15a, the hydrophobic porous film 14 is deformed, and the gas-side flow path becomes narrow. Therefore, the width of the groove 15a is 200 to
Preferably it is 1000 μm.

If the depth of the groove 15a is smaller than 100 μm, the gas and the condensed water do not flow sufficiently, so that the gas-liquid contact efficiency is reduced and it is difficult to sufficiently discharge the condensed water. On the other hand, the depth of the groove 15a is 500 μm
If it is larger than this, the thickness of the gas-side flow path member 15 increases, and therefore, the spiral-type gas-liquid contact membrane element 10
This is uneconomical because the diameter of the material increases and the material cost increases. In addition, the installation space is increased, which is uneconomical. Therefore, it is preferable that the depth of the groove 15a is 100 to 500 μm.

Further, when the width of the projections 15b between the grooves 15a is smaller than 250 μm, the strength of the gas-side flow path member 15 is reduced, and the projections due to the pressure of the liquid on the other surface side of the hydrophobic porous membrane 14 are reduced. The portion 15b may be crushed. on the other hand,
If the width of the convex portion 15b is larger than 750 μm, the gas-side flow path becomes narrow, the gas-liquid contact efficiency decreases, and it becomes difficult to sufficiently discharge condensed water. Therefore, it is preferable that the width of the convex portion 15b is 250 to 750 μm.

When the spiral type gas-liquid contact membrane module 1 of FIG. 1 is operated, the pure water 30 passes through the liquid inlet 4, and is constituted by one end 3 of the cylindrical container 2 and the end face of the spiral type gas-liquid contact membrane element 10. Flows into the entrance space 3a. Then, as shown in FIG. 2, the liquid flows in the liquid side flow path 19 in the axial direction along the liquid side flow path member 13.

On the other hand, the ozone gas 25 is supplied from the gas inlet 11a into the gas supply pipe 11 as shown in FIG. Then, as shown in FIG. 3, the gas enters the gas-side flow path 18 through the supply hole 11 b on the side surface of the gas supply pipe 11, and flows spirally in the direction orthogonal to the gas supply pipe 11 along the gas-side flow path material. And the cylindrical space 18a inside the cylindrical container 2
Through the gas outlet 7 to the outside. By providing a plurality of gas outlets 7, the flow of the ozone gas 25 in the gas-side flow path 18 can be made uniform.

As shown in FIG. 2, at the gas-liquid contact portion 10 a of the spiral type gas-liquid contact membrane element 10, the ozone gas 25 flowing spirally in a direction substantially perpendicular to the gas supply pipe 11 and the gas supply pipe 11 Pure water 30 flowing
Are in contact with each other via the hydrophobic porous membrane 14. Thereby, the ozone gas 25 permeates through the hydrophobic porous membrane 14 and dissolves in the pure water 30 to generate ozone water 31.

The ozone water 31 flowing out from the end face of the spiral type gas-liquid contact membrane element 10 is, as shown in FIG.
Through the outlet space 5a formed by the other end 5 of the cylindrical container 2 and the end surface of the spiral type gas-liquid contact membrane element 10,
It is discharged from the gas solution outlet 6 to the outside.

As shown in FIG. 2, the liquid-side flow path 19 of the spiral-type gas-liquid contact membrane element 10 (see FIG. 3).
The water vapor 9 generated in the above passes through the hydrophobic porous membrane 14,
It condenses in the gas side flow path 18 (see FIG. 3). The condensed water 8 thus generated flows spirally together with the ozone gas 25 along the groove 15 a of the gas-side flow path member 15 extending in a direction substantially perpendicular to the gas supply pipe 11, and is discharged from the gas outlet 7. . In this case, since the groove 15a extends linearly to the outer peripheral portion of the spiral type gas-liquid contact membrane element 10, the condensed water 8 can quickly flow to the outer peripheral portion.

As a result, the condensed water 8 does not stay in the gas side channel 18, so that the effective film area of the hydrophobic porous film 14 that contributes to the gas-liquid contact operation by the ozone gas 25 and the pure water 30 does not decrease. Therefore, the ozone water concentration does not decrease. In addition, since the pressure loss of the gas-side flow path 18 due to the condensed water 8 is prevented, the pressure of the gas-side flow path 18 does not become higher than the pressure of the liquid-side flow path 19, and bubbles are generated in the liquid-side flow path 19. No problem occurs.

[0057]

[Evaluation of gas-side flow path material] As a first gas-side flow path material (inward of the groove), a wire diameter of 2 in the direction parallel to the groove 15a was used.
A warp yarn of 50 μm is used, a weft yarn having a wire diameter of 60 μm is used in a direction perpendicular to the groove 15a, and P and
Using an FA filament, the width of the groove 15a is 400 μm.
m, the depth of the groove 15a is 250 μm, the width of the projection 15b is 500 μm, and the thickness is 370 μm. The woven fabric having the structure shown in FIG. A stack was made. As the second gas-side flow path material (outward of the groove), one in which two of the above woven fabrics were stacked with the groove structure surface facing outward was prepared. As a third gas-side flow path material (without grooves), a single plain weave flow path material having a fiber diameter of 250 μm and 25 mesh, in which no groove was provided, was prepared. As the fourth gas-side channel material (double-sided groove structure),
A warp yarn having a wire diameter of 250 μm is used in a direction parallel to the groove portion, a weft yarn having a wire diameter of 80 μm is used in a direction perpendicular to the groove portion, new PFA is used as the material of the warp yarn and the weft yarn, and the width of the groove portion is set to 40.
0 μm, groove depth 250 μm, protrusion width 500 μm
A piece of woven fabric having a thickness of 800 μm and having grooves on both sides was prepared.

Using the evaluation cell C10T- manufactured by Nitto Denko Corporation, the gas flow rate (ml / min) and the pressure of the gas-side flow path material during condensation were measured for the first to fourth gas-side flow path materials. The relationship with the loss (mmHg) was measured, and the results are shown in FIG.

As shown in FIG. 7, in the first and second gas-side flow path members, the pressure loss was lower than in the third and fourth gas-side flow path members, and good results were obtained. In addition, it was found that the pressure loss of the first gas-side flow path material was lower than that of the second gas-side flow path material, and that the pressure loss could be further reduced by overlapping the grooved structures with the inner surfaces facing inward.

[Embodiment] The above-mentioned first material was used as the gas-side channel material.
PTFE as hydrophobic porous membrane
A spiral-type gas-liquid contact membrane module having the structure shown in FIG. 1 was manufactured using the hydrophobic porous membrane NTF1122. The size of the membrane module is 84 m in diameter of the body.
m, length is 310mm, effective membrane area is about 0.5m
²

A 10% by volume ozone gas is supplied from the gas inlet 11a at a flow rate of 1 L / min.
5 ° C pure water at a pressure of 1 kgf / cm ² and a flow rate of 5 L / m
in, the ozone water concentration, the gas flow rate in the gas-side flow path, and the pressure loss (pressure loss during condensation) were measured.

[Comparative Example] The above-described third material was used as the gas-side channel material.
A spiral-type gas-liquid contact membrane module having the same structure as that of the example except that the gas-side channel material was used was produced. The size of the membrane module and the effective membrane area are the same as in the embodiment. Then, pure water and ozone gas were supplied under the same conditions as in the example, and the ozone water concentration and the pressure loss of the gas-side flow path were measured.

FIG. 8 shows the operation results of the spiral type gas-liquid contact membrane modules of the example and the comparative example. L1 is the ozone water concentration of the example, and L2 is the ozone water concentration of the comparative example.
L3 is the pressure loss in the gas side flow path of the embodiment, L3
Reference numeral 4 denotes a pressure loss in the gas-side flow channel of the comparative example.

As shown in FIG. 8, in the spiral-type gas-liquid contact membrane module of the comparative example, condensed water cannot be discharged out of the membrane module, and the pressure loss in the gas side flow path increases with time. The ozone water concentration also decreased from the initial level.
On the other hand, in the spiral type gas-liquid contact membrane module of the embodiment, since the condensed water can be constantly discharged to the outside of the membrane module, the pressure loss and the ozone water concentration in the gas side flow path do not change with time, and the performance is stable. showed that.

As described above, according to the spiral-type gas-liquid contact membrane module of the present invention, condensed water does not stay in the gas-side flow path, the effective membrane area does not decrease, and the pressure loss in the gas-side flow path does not increase. Long-term stable performance is obtained.

[Brief description of the drawings]

FIG. 1 is an axial sectional view showing a spiral-type gas-liquid contact membrane module according to an embodiment of the present invention.

FIG. 2 is a partially cutaway perspective view of a spiral-type gas-liquid contact membrane element in the spiral-type gas-liquid contact membrane module of FIG. 1;

FIG. 3 is a sectional view taken along line AA in FIG. 1;

FIG. 4 is an enlarged sectional view of a sealing portion of the spiral type gas-liquid contact membrane element of FIG.

FIG. 5 is a schematic view showing an example of a gas-side flow path member shown in FIG.

FIG. 6 is an enlarged cross section of a portion B shown in FIG.

FIG. 7 is a diagram showing a measurement result of a relationship between a gas flow rate of first to fourth gas-side flow path members and a pressure loss of the gas-side flow path material during condensation.

FIG. 8 is a diagram illustrating operation results of spiral-type gas-liquid contact membrane modules of an example and a comparative example.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Spiral type gas-liquid contact membrane module 2 Cylindrical container 3a Inlet space 4 Liquid inlet 5a Exit space 6 Gas solution outlet 7 Gas outlet 10 Spiral type gas-liquid contact membrane element 10b, 10c Sealing part 11 Gas supply pipe 11a Gas inlet 13 Liquid-side flow path material 14 Hydrophobic porous membrane 15 Gas-side flow path material 15a Groove 18 Gas-side flow path 18a Cylindrical space 19 Liquid-side flow path 21a Inner peripheral sealing part 21b Outer peripheral sealing part

Claims (11)

[Claims] 1. A spiral-type gas-liquid contact membrane element formed by superposing a permeable membrane and a flow path material and spirally winding the outer peripheral surface of a perforated hollow tube, wherein the flow path A spiral-type gas-liquid contact membrane element, wherein a plurality of gas-side flow path members provided with grooves along the gas flow direction are used as members. 2. The spiral gas-liquid contact membrane element according to claim 1, wherein the groove is provided on one surface of the gas-side flow path member. 3. The spiral-type gas-liquid contact membrane element according to claim 1, wherein the gas-side flow path members are arranged such that the grooves face each other. 4. The spiral gas-liquid contact membrane element according to claim 1, wherein said groove has a continuous shape. 5. The spiral type gas-liquid contact membrane element according to claim 1, wherein the groove has a linear shape. 6. The spiral gas-liquid contact membrane element according to claim 1, wherein the gas-side flow path member is made of a woven or knitted fabric. 7. The thickness of one sheet of the gas-side channel material is 200.
μm or more and 700 μm or less, and the width of the groove is 200 μm or less.
μm or more and 1000 μm or less, and the depth of the groove is 1
The spiral-type gas-liquid contact membrane element according to any one of claims 1 to 6, wherein the width of the convex portion between the grooves is from 250 µm to 750 µm. 8. The spiral gas-liquid contact membrane element according to claim 1, wherein the gas-side flow path member is made of a fluororesin. 9. The permeable membrane is composed of one or more pairs of continuous or independent porous membranes, and the porous membrane sandwiches the liquid-side channel material on the inside and the gas-side channel material on the outside. Overlapping and spirally wound on the outer peripheral surface of the perforated hollow tube, the inner peripheral side and outer peripheral side of the liquid-side flow path formed by the liquid-side flow path material between the porous membranes The side part is sealed, and both ends of the gas-side channel formed by the gas-side channel material between the porous membranes are sealed. 3. The spiral-type gas-liquid contact membrane element according to item 1. 10. A spiral-type gas-liquid contact membrane module, wherein the spiral-type gas-liquid contact membrane element according to claim 1 is housed in a container. 11. An outer peripheral surface of a perforated hollow tube in which one or a plurality of pairs of continuous or independent porous membranes are sandwiched between a first channel material inside and a second channel material is stacked outside. Spiral-type gas-liquid contact membrane element is formed by spirally winding the first channel member formed by the first channel member between the porous membranes. The side part on the outer peripheral side is sealed, and the second
Both ends of a second flow path formed by the flow path material are sealed, the spiral-type gas-liquid contact membrane element is housed in a cylindrical container, and the cylindrical container has first ends at both ends.
And a second fluid port at least at one end and an outer peripheral portion, and a first fluid port formed at both ends of the spiral type gas-liquid contact membrane element in the cylindrical container. The space and the second space formed on the outer peripheral side of the spiral type gas-liquid contact membrane element are separated,
The first space communicates with the first fluid port, and the second space
The space communicates with the second fluid port on the outer peripheral portion of the cylindrical container, and the inside of the perforated hollow tube communicates with the second fluid port on at least one end of the cylindrical container, As the gas-side flow path material through which the gas flows out of the first and second flow path materials, a plurality of gas-side flow path materials provided with grooves along the flow direction of the gas are stacked and used. Spiral type gas-liquid contact membrane module.